Nitric oxide and oxygen reactions with 1-butene over manganese(III) oxide

Reactions of 1-butene with nitric oxide from 623 to 723 K and with oxygen from 433 to 573 K have been studied in a differential flow system over manganese(III) oxide. Nitrous oxide was formed in the reaction of the hydrocarbon with nitric oxide along with products of complete combustion. The apparent activation energies were respectively 69 ± 4, 78 ± 4, and 30 ± 4 kJ mol −1 for nitrogen, carbon dioxide, and nitrous oxide reaction rates. The corresponding pre-exponential factors were 1.72 × 10 −1 and 1.16 mol 0.5 L −0.5 m 2 g −1 , and 1.99 × 10 −2 mol −0.35 L 0.35 m 2 g −1 . In the reaction with oxygen, apparent activation energies of 183 ± 4, 523 to 503 K, and 88 ± 4 kJ mol −1 , 503 to 433 K, were determined with pre-exponential factors 1.74 × 10 15 and 2.94 × 10 5 mol 0.3 m −2 g −1 . During catalysis the oxide underwent a partial phase change from α to γ in both reactions. Additionally, nitrate species were present on the surface after oxidation with nitric oxide. Kinetic expressions have been derived and mechanisms proposed for both reactions which may occur in emission control systems requiring the removal of NO x and unburned hydrocarbons.